Semiconducting Properties and Phase-Matching Nonlinear Optical

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Semiconducting properties and phase-matching nonlinear optical response of the one-dimensional selenophosphates ANb2PSe10 (A = K, Rb, and Cs) Jonathan C. Syrigos, Daniel J Clark, Felix O Saouma, Samantha M Clarke, Lei Fang, Joon I. Jang, and Mercouri G. Kanatzidis Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/cm5038217 • Publication Date (Web): 12 Dec 2014 Downloaded from http://pubs.acs.org on December 15, 2014

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Chemistry of Materials

Semiconducting properties and phase-matching nonlinear optical response of the one-dimensional selenophosphates ANb2PSe10 (A = K, Rb, and Cs) Jonathan C. Syrigos,† Daniel J. Clark,‡ Felix O. Saouma,‡ Samantha M. Clarke, † Lei Fang,† Joon I. Jang,‡ and Mercouri G. Kanatzidis*† AUTHOR ADDRESS †Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States ‡Department of Physics, Applied Physics and Astronomy, State University of New York (SUNY) at Binghamton, Binghamton, New York 13902, United States KEYWORDS: Crystal packing, chalcophosphates, chalcogenides, thiophosphates, flux synthesis, one-dimensional, semiconducting, metal-metal bond, microfibers, Nb2Se9, NbSe2

ABSTRACT: The new compounds ANb2PSe10, where A = K, Rb and Cs, form from polyselenophosphate flux reactions and crystallize in the noncentrosymmetric space group Pc. They feature infinite one-dimensional 1/∞[Nb2PSe10-] chains separated by alkali cations. The chains consist of [Nb2(Se2)2]4+ clusters bridged by a diselenide and a [PSe4]3- group. The chains pack differently depending on which alkali cation is present in the lattice. As a result, the analogs are not isostructural with respect to each other, and each has a different unit cell. The reaction

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chemistry involving a multitude of reaction conditions and their respective products is discussed. Other products from these reactions include NbSe3 and Nb2Se9 in both crystalline and microfibrous morphologies. The ANb2PSe10 compounds are stable to oxidation in ambient air but decompose when heated above 350 °C. Their band gaps were measured to be 1.1-1.2 eV and the resistivity of the K analog at room temperature was measured at 4.5 Ω-cm. Nonlinear optical second harmonic generation measurements were done on the Rb analog yielding a χ(2) of ~ 7 pm/V and showing phase matching behavior.

INTRODUCTION Complex metal chalcophosphates display a variety of interesting physico-chemical characteristics including reversible crystal-to-glass phase transitions,1, photoluminescence,5, generation (SHG).2,

6

2

ferroelectricity,3,

4

super-ionic conduction,7 metallic conductivity8 and second harmonic

5, 9, 10

These materials present a wide array of structural features ranging

from molecular units to 3-D networks3,

10

reflecting the rich diversity of chalcophosphate

building blocks that differ in size and shape. Examples of building blocks range from simple molecular units such as [PSe4]3-, [P2Se6]4- and [P2Se9]4- to clusters such as [P4Se10]4- to infinite chains like 1/∞[PSe3-] , 1/∞[P3Se4-] and 1/∞[PSe6-].3, 6, 11, 12 Despite the extensive research done on alkali metal late transition metal chalcophosphates, few reports exist on such compounds with early transition metals, especially selenium.5, 11, 13, 14-18 In fact, Sc, Mo, W, and Re do not have any respective chalcophosphate compounds. Some notable early transition metal quaternary chalcophosphates include NaV1-xP2S6 and KCrP2S6 which are composed of [V1-xP2S6]- and [CrP2S6]- chains respectively.18,

19

These compounds disperse in N-methylformamide (NMF)


2

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yielding gels. When dispersed in NMF, the V compound forms a vivid purple gel that exhibits liquid-crystalline behavior under the right conditions.19 Other examples are RbZrPSe6 and CsZrPSe6, which contains 1/∞[ZrPSe6-] chains and possesses a high SHG coefficient above that of AgGaSe2, a standard of SHG and photoluminescence.6 KxTaPS6 (x ≤ 0.5) is also an interesting compound as the amount of K intercalated in the phase changes the length of the Ta-Ta bond present in the compound.15 K3Cr2P3S12 contains [Cr2P3S12]3- chains with Cr-Cr dimers that magnetically order below 7 K.18 Here we present three new Nb selenophosphate compounds of the family ANb2PSe10 (where A = K, Rb and Cs). These materials have a noncentrosymmetric structure similar to those of the Rb and Cs containing sulfur analogs.16, 20 The ANb2PSe10 compounds feature infinite chains that pack differently depending on which alkali metal serves as the counterion. The band gaps for each analog were measured at ~1.1 eV, and the room temperature resistivity of the K analog was measured to be 4.5 Ω-cm displaying a thermally activated temperature dependence. The compounds exhibit a significant nonlinear optical (NLO) response with phase matchable second harmonic generation (SHG).

EXPERIMENTAL SECTION Reagents. All reagents were used as obtained from the specified supplier: potassium metal (98%, Sigma Aldrich, St. Louis, MO); rubidium metal (99.9+%, Strem Chemicals, Inc., Newburyport, MA); cesium metal (99.9+%, Strem Chemicals, Inc., Newburyport, MA); niobium metal powder (99.8% excluding Ta, Ta 3000 nm,41 which is also supported by the relatively flat trend of the particle size dependence in Figure 13b. Therefore, the SHG coefficient of 2 was estimated by directly comparing the reference material in the phase-matching regime as detailed below. AgGaSe2 is the benchmark mid-IR NLO material with a static SHG coefficient of χ(2) = 66 pm/V (λ → ∞).42 By using AgGaSe2 as a reference material with a known χ(2) value, the χ(2) of 2 was measured by comparing the SHG response at the static range in which both the reference and sample are phase-matchable with minimal absorption effects. Using the Kurtz powder method,43 the static value of χ(2) of 2 can be calculated by comparison with the reference;

where IS and IR are the experimentally measured SHG counts from the sample and reference, respectively (Figure 14). The calculation yields that χ(2)(RbNb2PSe10) ~ 7 pm/V.

CONCLUSIONS New semiconducting compounds KNb2PSe10, RbNb2PSe10 and CsNb2PSe10 consisting of 1

/∞[ Nb2PSe10-] chains form from reactions in polyselenophosphate fluxes. The orientation of the

chains with respect to the unit cells differs between the alkali salts, but the overall chemical structure is otherwise similar and noncentrosymmetric in nature. The compounds possess band


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gaps of ∼1.1-1.2 eV and decompose when heated above 350 °C. SHG analysis of the Rb analog states that it is phase-matchable with a χ(2) of ~ 7 pm/V. The ANb2PSe10 system shows the subtle but interesting effect that alkali metal counterion size can have on chain packing. While many materials simply expand their lattice parameters or change their crystallization completely,44 this system changes its chain packing instead. Finally, it is interesting that more elemental selenium and less alkali selenide in the reaction mixture defines a new method for the production of Nb2Se9 and NbSe2. Reducing the alkali selenide further while adding more elemental selenium favors formation of NbSe3 and Nb2Se9. When the relative fractions of Nb and Se increase in the reaction mixture at higher temperatures, the morphology of NbSe2 and Nb2Se9 changes to microfibers. This implies that this type of reaction may also be used as a convenient procedure to produce high yield samples of these binary materials in microfibrous form.

ASSOCIATED CONTENT Supporting Information. 31

P MAS Solid State NMR, the coordination environment of Rb+ in RbNb2PSe10, TEM of

CsNb2PSe10 crystallites from an isopropanol dispersion, magnetic susceptibility data, PXRD of DTA products and crystallographic information files (CIF) can be found in the supporting information. This material is available free of charge via the internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *[email protected]


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Author Contributions The manuscript was written through contributions of all authors. SHG section and data by Daniel J. Clark, Felix O. Saouma and Professor Joon I. Jang. Magnetic susceptibility data by Samantha M. Clarke and Professor Danna Freedman. Resistivity data by Lei Fang. All authors have given approval to the final version of the manuscript. Funding Sources NSF-NSEC, NSF-MRSEC, Keck Foundation, the State of Illinois, and Northwestern University Notes The authors declare no competing financial interest. ACKNOWLEDGMENT Financial support from the National Science Foundation (Grant DMR- 1410169) and from the Nicholson Fellowship is gratefully acknowledged. The authors thank Amy Sargeant for the help solving the crystal structures of KNb2PSe10 and CsNb2PSe10 and for general guidance in crystallography. This work made use of the EPIC facility (NUANCE Center-Northwestern University), which has received support from the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the Nanoscale Science and Engineering Center (NSF EEC–0647560) at the International Institute for Nanotechnology; and the State of Illinois, through the International Institute for Nanotechnology. NUANCE Center is supported by the NSF-NSEC, NSF-MRSEC, Keck Foundation, the State of Illinois, and Northwestern University. We thank Professor Danna Freedman for use of her magnetic susceptibility measurement system and for useful discussions.


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ABBREVIATIONS DMF, N,N-dimethylformamide; DTA, Differential Thermal Analysis; EDS, Energy Dispersive x-ray Spectroscopy; HU, Harmonics Unit; NLO, Nonlinear Optical; NMF, N-methylformamide; OPO, Optical Parametric Oscillator; SEM, Scanning Electron Microscopy; SHG, Second Harmonic Generation; PXRD, Powder X-Ray Diffraction; TEM, Transmission Electron Microscopy; TGA, Thermogravimetric Analysis

REFERENCES 1.

(a) Kanatzidis, M. G.; Sutorik, A. C., Progress in Inorganic Chemistry, 1995, 43, 151-

265; (b) Kanatzidis, M. G., Current Opinions in Solid State and Materials Science, 1997, 2, 139149. 2.

Evenson C. R.; Dorhout, P. K., Inorganic Chemistry, 2001, 40, 2875-2883.

3.

Chondroudis, K.; Kanatzidis, M. G., Inorganic Chemistry, 1995, 34, 5401-5402.

4.

Scott, B.; Pressprich, M.; Willet, R. D.; Cleary, D. A., Journal of Solid State Chemistry,

1992, 96, 294-300. 5.

Banerjee, S.; Szarko, J. M.; Yuhas, B. D.; Malliakas, C. D.; Chen, L. X.; Kanatzidis, M.

G., Journal of the American Chemical Society, 2010, 132, 5348-5350. 6.

Banerjee, S.; Malliakas, C. D.; Jang, J. I.; Ketterson, J. B.; Kanatzidis, M. G., Journal of

the American Chemical Society, 2008, 130, 12270-12272. 7.

(a) Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.;

Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.; Mitsui, A., Nature Materials, 2011, 10, 682686; (b) Ong, S. P.; Mo, Y. F.; Richards, W. D.; Miara, L.; Lee, H. S.; Ceder, G., Energy and Environmental Science, 2013, 6, 148-156.


22

Page 23 of 42

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


8.

Chung, I.; Biswas, K.; Song, J.-H.; Androulakis, J.; Chondroudis, K.; Paraskevopoulos,

K. M.; Freeman, A. J.; Kanatzidis, M. G.; Angewandte Chemie International Edition, 2011, 50, 8834-8838. 9.

Chung, I.; Malliakas, C. D.; Jang, J. I.; Canlas, C. G.; Weliky, D. P.; Kanatzidis, M. G. ,

Journal of the American Chemical Society, 2007, 129, 14996-15006. 10.

Chung, I.; Kanatzidis, M. G.; Chemistry of Materials, 2014, 26, 849-869.

11. Do, J.; Yun, H. , Inorganic Chemistry, 1996, 35, 3729-3730. 12. (a) McCarthy, T. J.; Kanatzidis, M. G., Inorganic Chemistry, 1995, 34, 1257-1267; (b) Song, J.-H.; Freeman, A. J.; Bera, T. K.; Chung, I.; Kanatzidis, M. G., Physical Review B, 2009, 79, 245203; (c) Chondroudis, K.; Kanatzidis, M. G., Inorganic Chemistry, 1998, 37, 2098-2099; (d) Chondroudis, K.; Kanatzidis, M. G., Angewandte Chemie International Edition, 1997, 36, 1324-1326. 13. (a) Mueller, C.; Joergens, S.; Mewis, A., Zeitschrift fuer Anorganische und Allgemeine Chemie, 2007, 633, 1633-1638; (b) Gutzmann, A.; Naether, C.; Bensch, W., Acta Crystallographica E, 2004, 60, i42-i44; (c) Cieren, X.; Angenault, J.; Couturier, J.C.; Jaulmes, S.; Quarton, M.; Robert, F., Journal of Solid State Chemistry, 1996, 121, 230-235; (d) Do, J.; Lee, K.; Yun, H., Journal of Solid State Chemistry, 1996, 125, 30-36; (e) Wu, Y. D.; Bensch, W., Inorg. Chem., 2007, 46, 6170-6177; (f) Gutzmann, A.; Naether, C.; Bensch, W., Solid State Sciences, 2004, 6, 205-211; (g) Gutzmann, A.; Naether, C.; Bensch, W., Acta Crystallographica C, 2004, 60, i11-i13; (h) Gutzmann, A.; Naether, C.; Bensch, W., Acta Crystallographica E, 2005, 61, i6-i8; (i) Gutzmann, A.; Naether, C.; Bensch, W., Acta Crystallographica E, 2005, 61, i20-i22; (j) Durand, E.; Evain, M.; Brec, R., Journal of Solid State Chemistry, 1993, 102, 146155; (k) Derstroff, V.; Tremel, W., Chemical Communications, 1998, 913-914; (l) Kopnin, E.; Coste, S.; Jobic, S.; Evain, M.; Brec, R., Materials Research Bulletin, 2000, 35, 1401-1410; (m) Gutzmann, A.; Naether, C.; Bensch, W., Zeitschrift fuer Anorganische und Allgemeine Chemie, 2005, 631, 524-529; (n) Kwak, J.-E.; Kim, C.; Yun, H.; Do, J., Bulletin of the Korean Chemical Society, 2007, 28, 701-704; (o) Jung-Eun, K.; Hoseop, Y., Bulletin of the Korean Chemical Society, 2008, 29, 273-275; (p) Kwan, D. Y.; Sangrok, K.; Hoseop, Y., Acta Crystallographica C, 2005, 61, i25-i26; (q) Sojeong, P.; Hoseop, Y., Acta Crystallographica E, 2010, 66, i51-i52;


23


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 42

(r) Eunsil, L.; Yonghee, L.; Hoseop, Y., Acta Crystallographica E, 2011, 67, i4; (s) Jaemin, Y.; Hoseop, Y., Acta Crystallographica E, 2011, 67, i24; (t) Gutzmann, A.; Bensch, W., Solid State Sciences, 2003, 5, 1271-1276; (u) Gutzmann, A.; Naether, C.; Bensch, W., Solid State Sciences, 2004, 6, 1155-1162; (v) Kwan, D. Y.; Sangrok, K.; Hoseop, Y.; Hanjo, L., Bulletin of the Korean Chemical Society, 2005, 26, 309-311; (w) Jin, H. B.; Youngmee, K.; Seri, K.; Jin, K. S., Journal of Solid State Chemistry, 2008, 181, 1798-1802; (x) Derstroff, V.; Ensling, J.; Ksenofontov, V.; Guetlich, P.; Tremel, W., Zeitschrift fuer Anorganische und Allgemeine Chemie, 2002, 628, 1346-1354; (y) Kyounghee, K.; Jooran, N.; Hoseop, Y., Acta Crystallographica E, 2010, 66, i65i65; (z) Menzel, F.; Brockner, W.; Carrillo Cabrera, W.; von Schnering, H.G., Zeitschrift fuer Anorganische und Allgemeine Chemie, 1994, 620, 1081-1086; (aa) Taylor, S. P.; Krawiec, M.; Hwu, S.-J., Acta Crystallographica C, 2002, 58, i27-i28. 14. Goh, E.-Y.; Kim, S.-J.; Jung, D., Journal of Solid State Chem. , 2002, 168, 119-125. 15. Do, J.; Dong, Y.; Kim, J.; Hahn, S.; Yun, H., Bulletin of the Korean Chemical Society, 2005, 26, 1260-1264. 16. Kim, C.-K.; Yun, H.-S., Acta Crystallographica Section C, 2002, 58, i53-i54. 17. Gutzmann, A.; Bensch, W., Solid State Sciences, 2002, 4, 835-840. 18. Coste, S.; Kopnin, E.; Evain, M.; Jobic, S.; Payen, C.; Brec, R., Journal of Solid State Chemistry, 2001, 162, 195-203. 19. Coste, S.; Gautier, E.; Evain, M.; Bujoli-Doeuff, M.; Brec, R.; Jobic, S.; Kanatzidis, M. G., Chemistry of Materials, 2003, 15, 2323-2327. 20. Jung-Eun, K.; Min, K. C.; Hoseop, Y.; Junghwan D., Bulletin of the Korean Chemical Society, 2007, 28, 701-704. 21. McCarthy, T. J.; Ngeyi, S. P.; Liao, J. H.; DeGroot, D. C.; Hogan, T.; Kannewurf, C. R.; Kanatzidis, M. G., Chem. Mater., 1993, 5, 331. 22. Mccarthy, T. J.; Kanatzidis, M. G., Inorg. Chem., 1995, 34, 1257. 23. Cie, Stoe &, X-AREA, X-RED, and X-SHAPE. Darmstadt, Germany, 1998.


24

Page 25 of 42

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


24. Sheldrick, G. M., Acta Crystallogr., Sect. A, 2008, 64, 112. 25. Jang, J. I.; Park, S.; Clark, D. J.; Saouma, F. O.; Lombardo, D.; Harrison, C. M.; Shim, B., Journal of the Optical Society of America, 2013, 30, 2292. 26. Trumboret, F. A.; ter Haar, L. W., Chemistry of Materials, 1989, 1, 490-492. 27. Meerschaut, A.; Guémas, L.; Berger R.; Rouxel, J., Acta Crystallographica B, 1979, 35, 1747-1750. 28. Sunshine, S. A.; Ibers, J. A., Acta Crystallographica C, 1987, 43, 1019-1022. 29. Sanjinés, R.; Berger, H.; Lévy, F., Materials Research Bulletin, 1988, 23, 549-553. 30. (a) Gieck, C.; Derstroff, V.; Block, T.; Felser, C.; Regelsky, G.; Jepsen, O.; Ksenofontov, V.; Gütlich, P.; Eckert, H.; Tremel, W., Chemistry - A European Journal, 2004, 10, 382-391; (b) Lee, E.; Lee, Y.; Yun, H., Acta Crystallographica Section E, 2011, E67, i4. 31. Do, J.; Yun, H., Inorg. Chem. , 1996, 35, 3729. 32. Camerel, P.; Gabriel, J.-C.; Batail, P.; Davidson, P.; Lemaire, B.; Schmutz, M.; GulikKrzywicki, T.; Bourgaux, C., Nano Letters, 2002, 4 (2), 403-407. 33. (a) Nye, J. F. , Physical Properties of Crystals: Their Representation by Tensors and Matrices. Clarendon Press; Oxford University Press: Oxford, Oxfordshire, NY, 1984; (b) Halasyamani, P. S.; Poeppelmeier, K. R. , Chem. Mater. , 1998, 10, 2753-2769. 34. O’Neal, S. C.; Pennington, W. T.; Kolis, J. W., Angewandte Chemie International Edition, 1990, 29, 1486-1488. 35. Canlas, C. G.; Kanatzidis, M. G.; Weliky, D. P., Inorganic Chemistry, 2003, 42, 33993405. 36. Sze, S. M.; Ng, Kwok K., Physics of Semiconductor Devices. John Wiley & Sons. 37. Morris, C. D.; Li, H.; Hosub Jin, H.; Malliakas, C. D.; Peters, J. A.; Trikalitis, P. N.; Freeman, A. J.; Wessels, B. W.; Kanatzidis, M. G., Chemistry of Materials, 2013, 25, 3344−3356.


25


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 42

38. Chaudhuri, S. P.; Patraa, S. K.; Chakraborty A. K., Journal of the European Ceramic Society, 1999, 19, 22941-2950. 39. UQG

Optics,

CORNING

PYREX®

7740

BOROSILICATE;

http://www.uqgoptics.com/materials_commercial_corning_pyrexBorosilicate.aspx,

(accessed

Oct. 17, 2014). 40. Jang, J. I.; Park, S.; Harrison, C. M.; Clark, D. J.; Morris, C. D.; Chung, I.; Kanatzidis, M. G., Optics Letters, 2013, 38, 1316. 41. Nikogosyan, D. N., Nonlinear Optical Crystals: A Complete Survey. Springer-Science: New York, 2005. 42. Bhar, G. C., Japanese Journal of Applied Physics Part I, Supplement 32-3, 1993, 32, 653. 43. Kurtz, S. K.; Perry, T. T., Journal of Applied Physics, 1968, 39, (3798). 44. Kim, K.-W.; Kanatzidis, M. G., Journal of the American Chemical Society, 1998, 120, 8124-8135.


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Table 1. Crystallographic refinement details of KNb2PSe10, RbNb2PSe10, and CsNb2PSe10. Compound

1

2

3

Empirical Formula

KNb2PSe10

RbNb2PSe10

CsNb2PSe10

Formula weight

1045.49

1091.86

1139.30

Wavelength, Å

0.71073

0.71073

0.71073

Habit

needle

needle

needle

Color

black

black

black

Crystal system

monoclinic

monoclinic

monoclinic

Space group

Pc

Pc

Pc

a, Å

7.2931(6)

7.3810(15)

14.626(3)

b, Å

15.612(2)

7.836(2)

7.810(2)

c, Å

13.557(3)

13.564(3)

13.553(3)

106.64(3)

106.75(3)

98.56(3)

1479.0(2)

751.2(3)

1530.9(5)

4

2

4

4.695

4.827

4.943

µ, mm

26.509

29.039

27.684

F(000)

1824

948

1968

θmax, deg

34.89

34.84

36.43

Reflections collected

22086

12251

24816

Rint

0.0710

0.0563

0.0550

No. parameters

253

128

β, (deg) V, Å

3

Z 3

ρ, g/cm

-1

254 2

Refinement method

Full matrix least-squares on F

GooF

1.063

1.055

1.085

Final R indices [>2σ(I)],

0.0571/0.1308

0.0461/0.1067

0.0577/0.1108

0.0728/0.1387

0.0600/0.1239

0.0820/0.1214

R1/wR2 R

indices

(all

data),

R1/wR2 R1 = Σ||Fo|-|Fc|| / Σ|Fo|. wR2 = {Σ[w(|Fo|2 - |Fc|2)2] / Σ[w(Fo2)2]1/2} and calc w=1/[σ2(Fo2)+(0.0559P)2+1.2737P] where P=(Fo2+2Fc2)/3


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Table 2. Selected bond lengths (Å) for ANb2PSe10 (A = K, Rb, and Cs) Atoms

KNb2PSe10

RbNb2PSe10

CsNb2PSe10

Nb(1)-Nb(2)

2.9589(14)

2.9675(11)

2.9626(11)

Nb(3)-Nb(4)

2.9661(14)

Nb(1)-Se(1)

2.762(2)

Nb(3)-Se(11)

2.766(2)

Nb(1)-Se(2)

2.776(2)

Nb(3)-Se(12)

2.770(2)

Nb(2)-Se(2)

2.770(2)

Nb(4)-Se(12)

2.776(2)

Nb(1)-Se(3)

2.717(2)

Nb(3)-Se(13)

2.732(2)

Nb(2)-Se(3)

2.688(2)

Nb(4)-Se(13)

2.676(2)

Nb(1)-Se(4)

2.710(2)

Nb(3)-Se(14)

2.707(2)

Nb(2)-Se(4)

2.707(15)

Nb(4)-Se(14)

2.702(2)

Nb(2)-Se(5)

2.712(2)

Nb(4)-Se(15)

2.714(2)

Nb(1)-Se(6)

2.656(2)

Nb(3)-Se(16)

2.645(2)

Nb(2)-Se(6)

2.613(2)

Nb(4)-Se(16)

2.598(2)

Nb(1)-Se(7)

2.602(2)

Nb(3)-Se(17)

2.621(2)

Nb(2)-Se(7)

2.642(2)

Nb(4)-Se(17)

2.649(2)

Nb(1)-Se(8)

2.618(2)

2.9647(12) 2.7738(15)

2.7244(15) 2.7102(15)

2.7823(15)

2.7770(14) 2.7687(14)

2.7737(14)

2.7841(12) 2.7816(13)

2.7300(14)

2.6829(13) 2.6807(14)

2.6814(15)

2.7349(14) 2.7311(14)

2.7076(13)

2.6914(13) 2.6990(13)

2.7040(13)

2.6969(13) 2.7011(13)

2.7158(15)

2.7471(15) 2.7709(15)

2.6563(15)

2.6624(15) 2.655(2)

2.6042(14)

2.6061(14) 2.6098(15)

2.616(2)

2.5957(15) 2.5976(15)

2.6541(14)

2.6648(15) 2.6572(15)

2.6062(13)


2.5963(14)

28

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Nb(3)-Se(18)

2.600(2)

Nb(2)-Se(8)

2.675(2)

Nb(4)-Se(18)

2.666(2)

Nb(1)-Se(9)

2.647(2)

Nb(3)-Se(19)

2.679(2)

Nb(2)-Se(9)

2.604(2)

Nb(4)-Se(19)

2.608(2)

Se(3)-Se(4)

2.328(2)

Se(13)-Se(14)

2.333(2)

Se(6)-Se(7)

2.293(2)

Se(16)-Se(17)

2.293(2)

Se(8)-Se(9)

2.312(2)

Se(18)-Se(19)

2.313(2)

Se(1)-P(1)

2.210(3)

Se(11)-P(2)

2.221(3)

Se(2)-P(1)

2.232(4)

Se(12)-P(2)

2.230(4)

Se(5)-P(1)

2.212(3)

Se(15)-P(2)

2.200(4)

Se(10)-P(1)

2.135(4)

Se(20)-P(2)

2.138(4)

2.5927(15) 2.6745(16)

2.6840(15) 2.660(2)

2.6731(14)

2.6635(14) 2.6691(14)

2.6053(14)

2.5925(15) 2.6063(15)

2.3318(14)

2.330(2) 2.329(2)

2.294(2)

2.297(2) 2.289(2)

2.315(2)

2.312(2) 2.309(2)

2.220(3)

2.200(3) 2.213(3)

2.236(3)

2.232(3) 2.231(3)

2.202(3)

2.206(3) 2.212(3)

2.137(3)


2.138(3) 2.133(3)

29


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Page 30 of 42

Table 3. Summary of reaction conditions and their respective products (A = K, Rb and Cs). Major products are shown in bold. Stoichiometric equivalents of Temperature (°C)

A2Sex

Nb

P2Se5

Se

Reaction Product

800

2

1

2

7,6

Nb2Se9, NbSe2

800

2

1

2

5-2

Nb2Se9, NbSe2, ANb2PSe10

800

1

1

2

5

Nb2Se9 (microfibers), ANb2PSe10

700

2

1

2

5-3

ANb2PSe10, NbSe2

700

1

4

1

7

NbSe3 (microfibers), ANb2PSe10

600

3

1

2

4

Unreacted flux, ANb2PSe10

600

4

1

2

4

Unreacted flux, ANb2PSe10, K4P2Se6

600

5

1

2

4

Unreacted flux, Nb2Se9, K4P2Se6

600

2, 1.5

1

2

4,3

ANb2PSe10


30

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Figure 1. Experimental powder X-ray diffraction patterns of ANb2PSe10 (A = K, Rb and Cs) compared to calculated patterns.

a)

b)

Figure 2. SEM images of Nb2Se9 microfibers at a a) lower resolution, and at b) a higher resolution. Microfibers range from 50 nm to 1 µm in width. The white dots present are flecks of selenium leftover from flux dissolution. Fleck formation can be easily prevented if the flux dissolution in DMF is kept oxygen free and the DMF is replaced every 30 min .


31


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Figure 3. PXRD patterns of RbNb2PSe10 freshly dispersed in H2O, isopropanol, and acetonitrile which were drop cast onto glass plates. The pattern shows that the samples still retain some crystallinity.

a)

b)


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Figure 4. a) A single chain of 1/∞[Nb2PSe10]- perpendicular to the chain direction. b) A single chain of 1/∞[Nb2PSe10]- looking down the chain direction.


33


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a)

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b)

Figure 5. a) RbNb2PSe10 along the [100] direction. b) RbNb2PSe10 along the [010] direction.


34

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a)

b)

Figure 6. a) RbNb2PSe10 along the [001] direction. b) A polyhedra view of the Nb center coordination environment. The bicapped trigonal prisms are outlined in black and are facesharing on one side and edge sharing on the other.


35


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

a)

Page 36 of 42

b)

Figure 7. a) KNb2PSe10 along the [010] direction. Notice that chains along the [010] direction do not perfectly overlap causing b to double. b) KNb2PSe10 along the [100] direction. The unit cell dimension b is doubled compared to the Rb and Cs analog.


36

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a)

b)

Figure 8. a) CsNb2PSe10 along the [010] direction. The unit cell dimension a is doubled compared to the K and Rb versions. The arrow depicts the chain slide of every other chain of the structure. b) CsNb2PSe10 along the [100] direction. Unlike K and Rb versions, it is impossible to align the chains perfectly in the crystal along the ac plane.


37


Figure 9. a) TGA of ANb2PSe10 (A = K, Rb, or Cs). All compounds oxidize slightly then decompose above 375 oC in air. Percent mass loss was calculated as (current mass)/(initial mass). b) DTA data of ANb2PSe10. No peaks were detected in all samples.

1

log(abs)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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0.75 0.5 KNb2PSe10 Eg = 1.19(2) eV RbNb2PSe10 Eg = 1.16(2) eV

0.25

CsNb2PSe10 Eg= 1.07(2) eV

1

2

3

4

5

E, eV

Figure 10. Optical absorption spectra of ANb2PSe10 (A = K, Rb, or Cs). The K analog band gap was measured to be around 1.19 eV, the Rb to be 1.15 eV, and the Cs band gap to be 1.07 eV.


38

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Figure 11. Resistivity vs temperature of a single crystal sample of KNb2PSe10. As the temperature decreases, the resistivity increases indicating semiconductor behavior. The room temperature resistivity was measured at 4.5 Ω-cm. Inset: the natural log of resistivity vs inverse temperature. The activation energy was obtained by fitting the linear portion.


39


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Page 40 of 42

Figure 12. SHG response as a function of wavelength from powder samples of (a) RbNb2PSe10 and (b) AgGaSe2 in the range of λinc = 2.3 – 4.1 µm.

Figure 13. Particle-size dependence of SHG in (a) RbNb2PSe10 and (b) AgGaSe2 at λ = 3.3 µm.


40

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Figure 14. SHG response comparison of RbNb2PSe10 with AgGaSe2. SHG counts were compared at the long-wavelength limit (1650 nm) where RbNb2PSe10 could be compared with AgGaSe2 fairly. The dotted lines signify where the SHG counts were compared for both compounds to obtain χ(2) of RbNb2PSe10.


41


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TOC Graphic


42

Semiconducting Properties and Phase-Matching Nonlinear Optical

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